Both the recent resurgence of infectious disease and the abiding interest in new tools for neuropharmacology have driven the continuing effort to isolate and establish the structures of new active agents from natural sources. While some of these might well be useful leads for pharmaceutical development, often the structurally more complex agents will not be pursued, because of perceived difficulties with their synthesis. An investigation of a new method for the construction of carbocyclic rings, intramolecular alkylidene C-H insertion, is proposed. This already shows the promise of becoming a powerful tool for target-directed synthesis. Specific targets include the cognition-enhancing alkaloid huperzine A, morphine, the parent compound of the morphine alkaloids, and N-deacetyllappaconitine, representative of the Delphinium diterpenoid alkaloids.